U.S. patent number 8,877,991 [Application Number 14/181,755] was granted by the patent office on 2014-11-04 for methods for the dehydrochlorination of 1,1,1,3-tetrachloropropane to 1,1,3-trichloropropene.
This patent grant is currently assigned to Honeywell International Inc.. The grantee listed for this patent is Honeywell International, Inc.. Invention is credited to Joshua Close, Robert Johnson, Hsueh Sung Tung, Terris Yang.
United States Patent |
8,877,991 |
Yang , et al. |
November 4, 2014 |
Methods for the dehydrochlorination of 1,1,1,3-tetrachloropropane
to 1,1,3-trichloropropene
Abstract
This invention relates to a method to improve
1,1,3-trichloropropene selectivity in HCC-250fb
(1,1,1,3-tetrachloropropane) dehydrochlorination. In normal
practice, FeCl.sub.3 is used as the catalyst for the
dehydrochlorination of HCC-250fb to produce 1,1,3-trichloropropene.
In this invention as source of water is added into the reaction
system to inhibit the formation of high boiling compounds such as
pentachlorocyclohexene and/or hexachlorocyclohexane. Once source of
water is H.sub.2O itself. Another source of water is one or more
hydrated metal halides.
Inventors: |
Yang; Terris (East Amherst,
NY), Tung; Hsueh Sung (Getzville, NY), Johnson;
Robert (Lancaster, NY), Close; Joshua (Blasdell,
NY) |
Applicant: |
Name |
City |
State |
Country |
Type |
Honeywell International, Inc. |
Morristown |
NJ |
US |
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Assignee: |
Honeywell International Inc.
(Morristown, NJ)
|
Family
ID: |
51351686 |
Appl.
No.: |
14/181,755 |
Filed: |
February 17, 2014 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20140235907 A1 |
Aug 21, 2014 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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61766380 |
Feb 19, 2013 |
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61766423 |
Feb 19, 2013 |
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Current U.S.
Class: |
570/228 |
Current CPC
Class: |
C07C
17/25 (20130101); C07C 17/25 (20130101); C07C
21/04 (20130101) |
Current International
Class: |
C07C
17/25 (20060101) |
Field of
Search: |
;570/228 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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787936 |
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Dec 1957 |
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GB |
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2013022806 |
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Feb 2013 |
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WO |
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Other References
PCT ISR & Written Opinion issued in PCT/US2014/016855 dated
Jul. 7, 2014. cited by applicant.
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Primary Examiner: Price; Elvis O
Attorney, Agent or Firm: Bradford; Bruce O.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims benefit of U.S. Provisional Patent
Application Ser. No. 61/766,380 filed Feb. 19, 2013, the disclosure
of which is hereby incorporated herein by reference.
This application also claims benefit of U.S. Provisional Patent
Application Ser. No. 61/766,423 filed Feb. 19, 2013, the disclosure
of which is hereby incorporated herein by reference.
Claims
What is claimed is:
1. A process for the catalytic dehydrochlorination of HCC-250fb to
produce 1,1,3-trichloropropene using a catalyst or catalyst mixture
comprising iron halides, wherein a source of water is added into
the system to inhibit the formation of high boiling compounds
including pentachlorocyclohexene and/or hexachlorocyclohexane.
2. The process of claim 1, wherein the source of water comprises
H.sub.2O.
3. The process of claim 2, wherein the iron halide compounds
comprise chloride compounds.
4. The process of claim 3, wherein the iron chloride compound
comprises FeCl.sub.3.
5. The process of claim 3, wherein the iron chloride compound
comprises FeCl.sub.2.
6. The process of claim 2, wherein the weight ratio of H.sub.2O to
HCC-250fb added into the system can be ranged from above 0% by
weight to 5% by weight.
7. The process of claim 2, wherein the weight ratio of H.sub.2O to
HCC-250fb is from about 0.01% to about 1%.
8. The process of claim 1, wherein the source of water comprises
one or more hydrated metal halides.
9. The process of claim 8, wherein the hydrated metal halide is
selected from the group consisting of BaCl.sub.2.2H.sub.2O,
CrCl.sub.3.6H.sub.2O, CuCl.sub.2.2H.sub.2O, FeCl.sub.2.4H.sub.2O,
FeCl.sub.3.6H.sub.2O, MnCl.sub.2.6H.sub.2O, NiCl.sub.2.6H.sub.2O,
SnCl.sub.2.2H.sub.2O, CoBr.sub.2.6H.sub.2O, VI.sub.3.6H.sub.2O and
mixtures thereof.
10. The process of claim 8, wherein the hydrated metal halide
comprises BaCl.sub.2.2H.sub.2O and the iron halide comprises
FeCl.sub.3.
11. The process of claim 10, wherein the weight ratio of FeCl.sub.3
to HCC-250fb is from above 0 to 10,000 ppm and the weight ratio of
BaCl.sub.2.2H.sub.2O to HCC-250fb is from above 0 to 10%.
12. The process of claim 10, wherein the weight ratio of FeCl.sub.3
to HCC-250fb is from 100 to 2000 ppm and the weight ratio of
BaCl.sub.2.2H.sub.2O to HCC-250fb is from 0.1% to 5%.
13. The process of claim 1, wherein the dehydrochlorination
reaction is carried out under conditions to attain a starting
material HCC-250fb conversion of at least about 20 mol % or
higher.
14. The process of claim 1, wherein the dehydrochlorination
reaction is carried out under conditions to attain a starting
material HCC-250fb conversion of at least about 40 mol % or
higher.
15. The process of claim 1, wherein the dehydrochlorination
reaction is carried out under conditions to attain a starting
material HCC-250fb conversion of at least about 50 mol % or
higher.
16. A process for the dehydrochlorination of HCC-250fb to produce
1,1,3-trichloropropene using one or more iron halide compounds as
the catalyst, wherein a source of water is added into the system to
improve 1,1,3-trichloropropene selectivity.
17. The process of claim 16, wherein the source of water comprises
H.sub.2O.
18. The process of claim 16, wherein the source of water comprises
one or more hydrated metal halides.
19. The process of claim 16, wherein the selectivity to the
formation of 1,1,3-trichloropropene is at least about 70 mol % or
higher.
20. The process of claim 16, wherein the selectivity to the
formation of 1,1,3-trichloropropene is at least about 95 mol % or
higher.
Description
BACKGROUND OF THE INVENTION
The compound 1,1,3-trichloropropene is useful as a chemical
intermediate in the formation of other commercially important
compounds. See, for example, U.S. Patent Pub. No. 2012-0142980, the
disclosure of which is hereby incorporated herein by reference.
SUMMARY OF THE INVENTION
This invention relates to a method to improve
1,1,3-trichloropropene selectivity in HCC-250fb
(1,1,1,3-tetrachloropropane) dehydrochlorination. In normal
practice, FeCl.sub.3 is used as the catalyst for the
dehydrochlorination of HCC-250fb to produce 1,1,3-trichloropropene.
See U.S. Patent Pub. No. 2012-0035402 A1, the disclosure of which
is hereby incorporated herein by reference.
It has been discovered that when using only FeCl.sub.3 as the
catalyst for the dehydrochlorination of HCC-250fb, the reaction
products contain significant amount of high boiling compounds,
("HBCs") such as pentachlorocyclohexene and/or
hexachlorocyclohexane species, in addition to the desired product,
namely 1,1,3-trichloropropene. While not wishing to be bound by
theory, it is believed that the formation of HBCs is due to the
dimerization of 1,1,3-trichloropropene.
Surprisingly, when a source of water was added into the
dehydrochlorination reaction HCC-250fb using FeCl.sub.3 as
dehydrochlorination catalyst, it was found that the selectivity to
1,1,3-trichloropropene was significantly improved. Further study
showed that, although H.sub.2O itself cannot perform as an
effective catalyst to dehydrochlorinate HCC-250fb to
1,1,3-trichloro-propene, the combination of FeCl.sub.3 and H.sub.2O
had a positive impact on the reduction of the formation of HBCs.
The selectivity to HBCs was reduced to zero when a source of
sufficient H.sub.2O was added into the system. These results proved
that a source of H.sub.2O can be used as an inhibitor to control
the formation of HBCs in the dehydrochlorination of HCC-250fb with
FeCl.sub.3 as the catalyst.
Thus, one embodiment of the present invention is directed to a
process for the dehydrochlorination of HCC-250fb to produce
1,1,3-trichloropropene using FeCl.sub.3 as the catalyst, wherein a
source of H.sub.2O is added into the system to inhibit the
formation of HBCs and to improve 1,1,3-trichloropropene
selectivity.
In certain embodiments, the process of the present invention
includes a feature wherein the weight ratio of H.sub.2O to
HCC-250fb added into the system ranges from above 0% by weight to
about 5% by weight, and preferably wherein the weight ratio of
H.sub.2O to HCC-250fb is from about 0.01% to 1%.
In addition to the use of water with the FeCl.sub.3 catalyst to
inhibit the formation of HBCs and to improve 1,1,3-trichloropropene
selectivity, it has been found that certain hydrated metal halides
can serve as a source of water, and can thus be employed as a
co-catalyst for FeCl.sub.3, to inhibit the formation of HBCs and to
improve 1,1,3-trichloro-propene selectivity. While not wishing to
be bound by theory, it is believed that the water from the hydrated
metal halides acts much in the same way as the direct addition of
water to the reaction, as described above, i.e., successfully
inhibiting the formation of HBCs and improving
1,1,3-trichloropropene selectivity.
Thus, another embodiment of the present invention is directed to a
process for the dehydrochlorination of HCC-250fb to produce
1,1,3-trichloropropene using a catalyst mixture containing
FeCl.sub.3 and a source of water comprising one or more hydrated
metal halides as a co-catalyst.
In certain embodiments, the hydrated metal halide co-catalyst
comprises BaCl.sub.2.2H.sub.2O. Applicant believes that any
hydrated metal halide will be useful herein, such as
CrCl.sub.3.6H.sub.2O, CuCl.sub.2.2H.sub.2O, FeCl.sub.2.4H.sub.2O,
FeCl.sub.3.6H.sub.2O, MnCl.sub.2.6H.sub.2O, NiCl.sub.2.6H.sub.2O,
SnCl.sub.2.2H.sub.2O, CoBr.sub.2.6H.sub.2O, VI.sub.3.6H.sub.2O or a
mixture thereof, can be used as a co-catalyst source of water for
the dehydrochlorination of HCC-250fb using FeCl.sub.3 as the
catalyst.
In certain embodiments, the weight ratio of FeCl.sub.3 to HCC-250fb
is from above 0 ppm to 10,000 ppm and the weight ratio of
BaCl.sub.2.2H.sub.2O to HCC-250fb is from above 0% to 10%.
In certain embodiments, the weight ratio of FeCl.sub.3 to HCC-250fb
is from 100 ppm to 2000 ppm and the weight ratio of
BaCl.sub.2.2H.sub.2O to HCC-250fb is from 0.1% to 5%.
It should be appreciated by those persons having ordinary skill in
the art(s) to which the present invention relates that any of the
features described herein in respect of any particular aspect
and/or embodiment of the present invention can be combined with one
or more of any of the other features of any other aspects and/or
embodiments of the present invention described herein, with
modifications as appropriate to ensure compatibility of the
combinations. Such combinations are considered to be part of the
present invention contemplated by this disclosure.
It is to be understood that both the foregoing general description
and the following detailed description are exemplary and
explanatory only and are not restrictive of the invention as
claimed. Other embodiments will be apparent to those skilled in the
art from consideration of the specification and practice of the
invention disclosed herein.
DETAILED DESCRIPTION OF THE INVENTION
As described above, it has been discovered that the addition of a
source of water selected from H.sub.2O and/or one or more hydrated
metal halide co-catalysts to the HCC-250fb dehydrochlorination
process using FeCl.sub.3 as the main catalyst can inhibit the
formation of unwanted HBCs and improve the selectivity to
1,1,3-trichloropropene significantly, which can be beneficial to
the reduction of process waste and simplify the future separation
of crude product, and therefore reduce the production cost.
The dehydrochlorination reactions are preferably carried out under
conditions to attain a HCC-250fb conversion of about 20 mol % or
higher, preferably about 40 mol % or higher, and even more
preferably about 50 mol % or higher, and a desired
1,1,3-trichloro-propene product selectivity of at least about 50
mol % or higher, preferably at least about 70 mol % or higher, and
more preferably at least about 95 mol % or higher. Selectivity is
calculated by number of moles of product formed divided by number
of moles of reactant consumed.
Useful reaction temperatures for the dehydrochlorination reactions
may range from about 50.degree. C. to about 300.degree. C.
Preferred temperatures may range from about 70.degree. C. to about
150.degree. C., and more preferred temperatures may range from
about 100.degree. C. to about 125.degree. C. One especially
preferred reaction temperature is about 120.degree. C. The reaction
may be conducted at atmospheric pressure, super-atmospheric
pressure or under vacuum. The vacuum pressure can be from about 0
torr to about 760 torr. Contact time of the reactant starting
materials with the catalyst mixture may range from about 1 to 10
hours, preferably from about 2 to 8 hours, more preferably about 4
hours, however, longer or shorter times can be used.
The following Table shows the result of testing done in accordance
with one embodiment of the present invention.
TABLE-US-00001 HCC-250fb Dehydrochlorination Reaction Temp,
.degree. C. Reaction Time, hr FeCl3/250fb, ppmw H2O/25fb, ppmw
250fb conv.,% mol 1,1,3 Sel., % mol HCH Sel., % mol 120 4 752 0
96.76% 91.42% 8.57% 120 4 756 1087 88.92% 96.10% 3.58% 120 4 745
2089 85.84% 97.11% 2.86% 120 4 743 2979 56.78% 99.46% 0.51% 120 4
796 3574 33.58% 100.00% 0.00%
In another embodiment, the hydrated metal halide
BaCl.sub.2.2H.sub.2O was tested as the dehydrochlorination catalyst
for HCC-250fb, with only 6.5% mol of 250fb conversion achieved
under reaction conditions of 120.degree. C., 8 hours of residence
time and 2.3% of BaCl.sub.2.2H.sub.2O/250fb weight ratio. While the
yield of 1,1,3-trichloropropene was low, there were no HBCs
detected in the reaction product.
Further study showed that, the combination of FeCl.sub.3 and
BaCl.sub.2.2H.sub.2O had both a positive impact on the selectivity
to 1,1,3-trichloropropene as well as a reduction of the formation
of HBCs. The addition of BaCl.sub.2.2H.sub.2O to the mixture of
HCC-250fb and FeCl.sub.3 reduced the selectivity to HBCs and
increased the selectivity to 1,1,3-trichloro-propene significantly.
These results proved that the mixture of FeCl.sub.3 and
BaCl.sub.2.2H.sub.2O can be used as an effective catalyst to
control the formation of HBCs in the dehydrochlorination of
HCC-250fb. It is expected that other hydrated metal halide
compounds will provide a similar effect.
The mixture of BaCl.sub.2.2H.sub.2O and FeCl.sub.3 can be used as
the catalyst for the dehydrochlorination of HCC-250fb to produce
1,1,3-trichloropropene, which can reduce the selectivity to HBCs
and improve the selectivity to 1,1,3-trichloropropene. As HBCs
cannot be converted into the desired product, the new catalyst
mixture will be beneficial to the reduction of process waste and
simplify the future separation of crude product, and therefore
reduce the overall production cost.
The following examples provide additional details regarding various
embodiments of the present invention.
Example 1
A 500 ml glass flask (reactor) equipped with a magnetic stirring
bar and a total condenser was charged with 150.8 g HCC-250fb
(Vulcan, 99.9 wt %) and 0.113 g FeCl.sub.3. The reactor was stirred
and heated to 120.+-.2.degree. C. via an oil bath. After 4 hours,
the reactor was removed from the oil bath and cooled down to room
temperature. Then the mixture in the reactor was filtered, washed
with deionized (D.I.) water and dried with MgSO.sub.4. By GC
analysis, the reaction mixture contained 81.1 wt % of
1,1,3-trichloropropene, 3.7 wt % of HCC-250fb, and 15.2 wt % of
HBCs, representing a HCC-250fb conversion of 96.8 mol %,
1,1,3-trichloropropene selectivity of 91.4 mol %, and HBCs
selectivity of 8.6 mol %.
Example 2
100.6 g HCC-250fb (Vulcan, 99.9 wt %) and 0.35 g D.I. H.sub.2O were
charged into the reactor with the same reaction conditions and
procedure followed as described in Example 1. By GC analysis, the
reaction mixture contained 0.5 wt % of 1,1,3-trichloro-propene and
99.5 wt % of HCC-250fb with no HBCs detected, representing a
HCC-250fb conversion of 0.6 mol % and 1,1,3-trichloropropene
selectivity of 100 mol %.
Example 3
The same apparatus as described in Example 1 was charged with 100.3
g HCC-250fb (Vulcan, 99.9 wt %), 0.076 g FeCl.sub.3 and 0.11 g D.I.
H.sub.2O. The same reaction conditions and procedure were followed
as in Example 1. By GC analysis, the reaction mixture contained
80.8 wt % of 1,1,3-trichloropropene, 13.1 wt % of HCC-250fb and 6.1
wt % of HBCs, representing a HCC-250fb conversion of 88.9 mol %,
1,1,3-trichloro-propene selectivity of 96.4 mol %, and HBCs
selectivity of 3.6 mol %.
Example 4
100.2 g HCC-250fb (Vulcan, 99.9 wt %), 0.08 g FeCl.sub.3 and 0.36 g
D.I. H.sub.2O were charged into the reactor with the same reaction
conditions and procedure followed as described in Example 1. By GC
analysis, the reaction mixture contained 28.8 wt % of
1,1,3-trichloropropene, 71.2 wt % of HCC-250fb with no HBCs
detected, representing a HCC-250fb conversion of 33.6 mol % and
1,1,3-trichloropropene selectivity of 100 mol %.
Example 5
100.7 g HCC-250fb (Vulcan, 99.9 wt %), 0.075 g FeCl.sub.3 and 0.3 g
D.I. H.sub.2O were charged into the reactor with the same reaction
conditions and procedure followed as described in Example 1. By GC
analysis, the reaction mixture contained 50.8 wt % of
1,1,3-trichloropropene, 48.6 wt % of HCC-250fb and 0.5 wt % of
HBCs, representing a HCC-250fb conversion of 56.8 mol %,
1,1,3-trichloropropene selectivity of 99.5 mol % and HBCs
selectivity of 0.5 mol %.
Example 6
The same apparatus as described in Example 1 was charged with 150.5
g HCC-250fb (Vulcan, 99.9 wt %) and 3.5 g BaCl.sub.2.2H.sub.2O. The
same reaction conditions and procedure were followed as in Example
1. By GC analysis, the reaction mixture contained 5.2 wt % of
1,1,3-trichloropropene and 94.8 wt % of HCC-250fb with no HBCs
detected, representing a HCC-250fb conversion of 6.5 mol % and
1,1,3-trichloropropene selectivity of 100 mol %.
Example 7
150.5 g HCC-250fb (Vulcan, 99.9 wt %), 0.117 g FeCl.sub.3 and 0.88
g BaCl.sub.2.2H.sub.2O were charged into the reactor with the same
reaction conditions and procedure followed as described in Example
1. By GC analysis, the reaction mixture contained 77.9 wt % of
1,1,3-trichloropropene, 15.7 wt % of HCC-250fb, and 6.3 wt % of
HBCs, representing a HCC-250fb conversion of 86.6 mol %,
1,1,3-trichloropropene selectivity of 96.1 mol %, and HBCs
selectivity of 3.9 mol %.
Example 8
150.1 g HCC-250fb (Vulcan, 99.9 wt %), 0.112 g FeCl.sub.3 and 3.5 g
BaCl.sub.2.2H.sub.2O were charged into the reactor with the same
reaction conditions and procedure followed as described in Example
1. By GC analysis, the reaction mixture contained 38.9 wt % of
1,1,3-trichloropropene, 47.3 wt % of HCC-250fb, and 0.02 wt % of
HBCs, representing a HCC-250fb conversion of 50.7 mol %,
1,1,3-trichloropropene selectivity of 99.9 mol %, and HBCs
selectivity of 0.03 mol %.
As used herein, the singular forms "a", "an" and "the" include
plural unless the context clearly dictates otherwise. Moreover,
when an amount, concentration, or other value or parameter is given
as either a range, preferred range, or a list of upper preferable
values and lower preferable values, this is to be understood as
specifically disclosing all ranges formed from any pair of any
upper range limit or preferred value and any lower range limit or
preferred value, regardless of whether ranges are separately
disclosed. Where a range of numerical values is recited herein,
unless otherwise stated, the range is intended to include the
endpoints thereof, and all integers and fractions within the range.
It is not intended that the scope of the invention be limited to
the specific values recited when defining a range.
It should be understood that the foregoing description is only
illustrative of the present invention. Various alternatives and
modifications can be devised by those skilled in the art without
departing from the invention. Accordingly, the present invention is
intended to embrace all such alternatives, modifications and
variances that fall within the scope of the appended claims.
* * * * *